Zero-Field Splitting in a Series of Structurally Related Mononuclear NiII
–Bispidine Complexes

Atanasov, Mihail; Comba, Peter; Helmle, Stefan; Müller, Dennis; Neese, Frank

doi:10.1021/ic3016047

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Zero-Field Splitting in a Series of Structurally Related Mononuclear Ni^II–Bispidine Complexes

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Atanasov, Mihail
Anorganisch-Chemisches Institut, Universität Heidelberg;
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences;

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Neese, Frank
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

Atanasov, M., Comba, P., Helmle, S., Müller, D., & Neese, F. (2012). Zero-Field Splitting in a Series of Structurally Related Mononuclear Ni^II–Bispidine Complexes. Inorganic Chemistry, 51(22), 12324-12335. doi:10.1021/ic3016047.

Cite as: https://hdl.handle.net/21.11116/0000-0007-E4E0-A

Abstract

The synthesis, single-crystal X-ray structures, electronic absorption spectra, and magnetic properties of six Ni^II complexes with a tetradentate (L¹) and three pentadentate (L², L³, L⁴) bispidine ligands (3,7-diazabicyclo[3.3.1]nonane derivatives), Ni(L¹·H₂O)(OH₂)₂](PF₆)₂, [Ni(L¹·H₂O)(O₂NO)]NO₃, [Ni(L¹·H₂O)(OOCCH₃)]PF₆, [Ni(L²·H₂O)NCMe](PF₆)₂, [Ni(L³·H₂O)OH₂](PF₆)₂, and [Ni(L⁴·H₂O)NCMe](PF₆)₂ are reported. The Ni–donor bonding to pyridine and tertiary amine groups and oxygen- or nitrogen-bound coligands, completing the octahedral coordination sphere of Ni^II, is analyzed using a combination of ab initio electronic structure calculations (complete active space self-consistent field, CASSCF, followed by N-electron valence perturbation theory, NEVPT2) and angular overlap ligand field analysis. Magnetic properties are rationalized with an analysis of the magnetic anisotropy in terms of zero-field splitting and g-tensor parameters, obtained from first principles, and their correlation with the Ni^II–donor bonding parameters from the ligand field analysis of the ab initio results. A two-dimensional spectrochemical series of the ligands considered, according to their σ and π bonding to Ni^II, is also derived.